There is a substantial body of literature directed to the use of various acid catalysts to effect intramolecular and intermolecular condensation of amino compounds. U.S. Pat. No. 2,073,671 and U.S. Pat. No. 2,467,205 constitute early prior work on the use of acid condensation catalysts to condense amino compounds. U.S. Pat. No. 2,073,671 discusses, in a general fashion, the catalytic intermolecular condensation of alcohols and amines or ammonia using the same phosphate catalysts later favored by U.S. Pat. No. 2,467,205 for the intramolecular condensation of amines. The two patents are not in harmony over the use of other materials as catalysts. To illustrate this point, U.S. Pat. No. 2,073,671 states:
"Alumina, thoria, blue oxide of tungsten, titania, chromic oxide, blue oxide of molybdenum and zirconia have been mentioned in the literature for use as catalysts in carrying out these reactions but their effectiveness is so low that no practical application has been made of their use." PA0 "silica gel, titania gel, alumina, thoria, boron phosphate, aluminum phosphate, and the like." PA0 ". . . a heated catalyst or contact mass containing phosphorus and especially one or more of the oxygen acids of phosphorus, their anhydrides, their polymers, and their salts; for example, orthophosphoric acid, metaphosphoric acid, Pyrophosphoric acid, phosphorous pentoxide, dimetaphosphoric acid, trimetaphosphoric acid, primary ammonium phosphate, secondary ammonium phosphate, normal ammonium phosphate, ammonium metaphosphate, secondary ammonium pyrophosphate, normal ammonium pyrophosphate, aluminum phosphate, aluminum acid phosphate and mixtures of two or more of such materials."
whereas U.S. Pat. No. 2,467,205 in describing the self-condensation of ethylenediamine (EDA) under vapor phase conditions, to initially produce ethyleneamines, but after recycle, eventually generates piperazine (PIP) through multistep condensation reactions, followed by deamination, recommends "dehydration catalysts" which are thereafter characterized as
U.S. Pat. No 2,073,671 describes the condensation catalyst in the following terms:
whereas U.S. Pat. No. 2,467,205 describes one of the preferred catalysts as "basic aluminum phosphate".
U.S. Pat. No. 2,454,404 describes the "catalytic deamination of alkylene polyamines" by reacting DETA vapor over solid catalysts such as activated alumina, bauxite, certain aluminum silicates such as kaolin and oxides of thorium, titanium and zirconium.
U.S. Pat. Nos. 2,073,671 and 2,467,205 demonstrate a common experience in using aluminum phosphate as a condensation catalyst to produce aliphatic amines, and U.S. Pat. Nos. 2,454,404 and 2,467,205 contemplate the other solid catalysts for deamination of amines to make heterocyclic noncyclic amines. In general, the reaction conditions under which deamination to effect cyclization occurs are more severe than those employed for condensation to generate noncyclic molecules, all other factors being comparable.
U.S. Pat. Nos. 4,540,822, 4,584,406 and 4,588,842 depict the use of Group IVB metal oxides as supports for phosphorus catalysts used to effect the condensation of amino compounds with alkanolamines.
U.S. Pat. No. 4,683,335 describes the use of tungstophosphoric acid, molybdophosphoric acid or mixtures deposited on titania as catalysts for the condensation of amines and alkanolamines to make polyalkylenepolyamines.
U.S. Pat. Nos. 4,314,083, 4,316,840, 4,362,886 and 4,394,524 disclose the use of certain metal sulfates as useful catalysts for the condensation of alkanolamine and an amino compound. No distinction is made between the sulfur compounds in respect to catalytic efficacy. Sulfuric acid is as good as any metal sulfate, and all metal sulfates are treated as equivalents. At column 8 of U.S. Pat. No. 4,314,083, it is noted that boron sulfate "gave extremely high selectivity at a low level" of EDA. However, selectivity in general was shown to increase with an increase of EDA relative to monoethanolamine (MEA) in the feed. The only specific metal sulfates disclosed in the patents are antimony sulfate, beryllium sulfate, iron sulfate and aluminum sulfate.
In the typical case of the manufacture of alkyleneamines, mixtures with other alkyleneamines (including a variety of polyalkylenepolyamines and cyclic alkylenepolyamines) are formed. The same holds true when the object of the process is to produce polyalkylenepolyamines whether acyclic or cyclic, in that a variety of amino compounds are also formed. Each of these cyclic and acyclic alkyleneamines can be isolated from the mixture.
The acid catalyzed condensation reaction involving the reaction of an alkanolamine with an amino compound in the presence of an acidic catalyst is believed to proceed through the mechanism of esterifying free surface hydroxyl groups on the acid catalyst with the alkanolamine and/or by protonating the alkanolamine in the presence of the acid catalyst, followed by loss of water and amine condensation of the ester or the hydrated species, as the case may be, to form the alkyleneamine. Illustrative prior art directed primarily to the cyclic polyalkylenepolyamines (heterocyclic polyamines), but not necessarily limited to the aforementioned acid condensation reaction, are: U.S. Pat. Nos. 2,937,176, 2,977,363, 2,977,364, 2,985,658, 3,056,788, 3,231,573, 3,167,555, 3,242,183, 3,297,701, 3,172,891, 3,369,019, 3,342,820, 3,956,329, 4,017,494, 4,092,316, 4,182,864, 4,405,784 and 4,514,567; European Patent Applications 0 069 322, 0 111 928 and 0 158 319; East German Pat. No. 206,896; Japanese Patent Publication No. 51-141895; and French Patent No. 1,381,243. The evolution of the art to the use of the acid catalyzed condensation reaction to generate acyclic alkyleneamines, particularly acyclic polyalkylenepolyamines, as the predominant products stemmed from the initial disclosure in U.S. Pat. No. 4,036,881, though earlier patent literature fairly well characterized such an effect without labeling it so, see U.S. Pat. No. 2,467,205, supra. The acid catalysts are phosphorus compounds and the reaction is carried out in the liquid phase. The trend in this catalyst direction was early set as demonstrated by U.S. Pat. Nos. 2,073,671 and 2,467,205, supra. A modification of this route includes the addition of ammonia to the reaction, see, for example, U.S. Pat. No. 4,394,524 and U.S. Pat. No. 4,463,193 for the purpose of converting alkanolamine such as MEA in situ to alkylene amine such as EDA by reaction with ammonia, and the EDA is in situ reacted with MEA according to the process of U.S. Pat. No. 4,036,881 to form alkyleneamines.
A summary of the prior art employing acid catalysts for making alkyleneamines is set forth in Table I below.
TABLE I __________________________________________________________________________ CITATION CATALYST TYPE REACTANTS __________________________________________________________________________ U.S. Pat. No. 2,467,205 Silica gel, titania gel, alumina Vapor phase condensation of thoria, aluminum phosphate. EDA over a fixed bed of the Preferred catalyst is basic catalyst, multipass process aluminum phosphate. shifts from polyethylene- polyamines with the first few cycles. U.S. Pat. No. 4,036,881 Phosphorus containing substances Alkanolamine and alkylene- selected from the group consisting amine in liquid phase of acidic metal phosphates, reaction. phosphoric acid compounds and their anhydrides, phosphorus acid compounds and their anhydrides, alkyl or aryl phosphate esters, alkyl or aryl phosphite esters, alkyl or aryl substituted phosphorous and phosphoric acids wherein said alkyl groups have from 1 to about 8 carbon atoms and said aryl groups have from 6 to about 20 carbon atoms, alkali metal monosalts of phosphoric acid, the thioanalogs of the fore- going, and mixtures of the above. U.S. Pat. No. 4,044,053 Phosphorus containing substances Alkanepolyols and alkylene- selected from the group consisting amine in liquid phase of acidic metal phosphates, reaction. phosphoric acid compounds and their anhydrides, phosphorus acid compounds and their anhydrides, alkyl or aryl phosphate esters, alkyl or aryl phosphite esters, alkyl or aryl substituted phosphorous acids and phosphoric acids wherein said alkyl groups have from 1 to about 8 carbon atoms and said aryl groups have from 6 to about 20 carbon atoms, alkali metal mono- salts of phosphoric acid and mixtures of the above. U.S. Pat. No. 4,314,083 Salt of a nitrogen or sulfur con- Alkanolamine and an taining substance or the corres- alkyleneamine in liquid ponding acid. phase reaction. U.S. Pat. No. 4,316,840 Metal nitrates and sulfates Reforming linear polyamines. including zirconium sulfate. U.S. Pat. No. 4,316,841 Phosphate, perferably boron Reforming linear polyamines. phosphate. U.S. Pat. No. 4,324,917 Phosphorus-containing cation Alkanolamine and an alkylene- exchange resin. amine in liquid phase reaction. U.S. Pat. No. 4,362,886 Arsenic, antimony or bismuth Alkanolamie and an alkylene- containing compounds. Antimony amine in liquid phase sulfate specifically disclosed. reaction. U.S. Pat. No. 4,399,308 Lewis acid halide. Alkanolamine and an alkylene- amine in liquid phase reaction. U.S. Pat. No. 4,394,524 Phosphorus-containing substance Ammonia, alkanolamine and an or salt of a sulfur-containing alkyleneamine in liquid phase substance, or the corresponding reaction. acid. U.S. Pat. No. 4,448,997 Reacts alumina with phosphoric EDA with MEA. acid, adds ammonium hydroxide. U.S. Pat. No. 4,463,193 Group IIIB metal acid phosphate. Ammonia, alkanolamine and an alkyleneamine. U.S. Pat. No. 4,503,253 Supported phosphoric acid. Ammonia, alkanolamine and an alkyleneamine. U.S. Pat. No. 4,521,600 Select hydrogen phosphates and Alkanolamine and an alkylene- pyrophosphates. amine. U.S. Pat. No. 4,524,143 Phosphorus impregnated onto Alkanolamine and an alkylene- zirconium silicate support. amine. U.S. Pat. No. 4,540,822 Phosphorus compound deposited Alkanolamine and an alkylene- on a Group IVB metal oxide amine, regenerates the support. catalyst with O.sub.2 -containing gas. U.S. Pat. No. 4,547,591 Silica-alumina alone or in An ethyleneamine and an combination with an acidic alkanolamine; ethyleneamines; phosphorus cocatalyst. or ammonia and an alkanol- amine. U.S. Pat. No. 4,550,209 An intercalatively catalytically EDA and MEA. active tetravalent zirconium polymeric reaction product of an organo phosphonic acid or an ester thereof with a compound of tetravalent zirconium reactive therewith. U.S. Pat. No. 4,552,961 Phosphorus amide compound. Alkyleneamine and alkanolamine and/or alkylene glycol. U.S. Pat. No. 4,555,582 Phosphorus chemically bonded to MEA and EDA. a zirconium silicate support. U.S. Pat. No. 4,560,798 Rare earth metal or strontium MEA. acid phosphate. U.S. Pat. No. 4,578,517 Group IIIB metal acid phosphate. Ammonia or p-/s-amine and alkanolamine. U.S. Pat. No. 4,578,518 Thermally activated, calcined, MEA and EDA. pelleted titania containing titanium triphosphate. ". . . the titania that was used was . . . anatase." (Col. 9, lines 18-19). U.S. Pat. No. 4,578,519 Thermally activated, calcined, MEA and EDA with optional pelleted titania with chemically recycle of DETA. bonded phosphorus derived from polyphosphoric acid. U.S. Pat. No. 4,584,405 Activated carbon, optionally MEA and EDA. treated to incorporate phosphorus. Activated carbon may be washed with strong mineral acid to remove impurities followed by water wash. Optional treatment follows. U.S. Pat. No. 4,584,406 Pelleted Group IVB metal oxide MEA and EDA. with chemically bonded phosphorus derived from phosphoryl chloride or bromide. U.S. Pat. No. 4,588,842 Thermally activated pelleted MEA and EDA. Group IVB metal oxide with chemically bonded phosphorus. U.S. Pat. No. 4,605,770 Group IIA or IIIB metal acid Alkanolamine and an phosphate. alkyleneamine "in liquid phase". U.S. Pat. No. 4,609,761 Thermally activated pelleted MEA and EDA. titania with chemically bonded phosphorus. U.S. Pat. No. 4,612,397 Thermally activated pelleted MEA and EDA. titania with chemically bonded phosphorus. U.S. Pat. No. 4,617,418 Acid catalysts, mentions "beryl- Ammonia, alkanolamine and lium sulfate". an alkyleneamine "under vapor phase conditions". Japanese Patent Variety of phosphorus and metal Ammonia, alkanolamine and Application phosphates including Group IVB ethyleneamine, with ammonia/ #1983-185,871, phosphates. alkanolamine molar ratio Publication greater than 11. #1985-78,945 U.S. Pat. No. 4,683,335 Tungstophosphoric acid, molybdo- Claims reaction of MEA and phosphoric acid or mixtures EDA, but discloses self- deposited on titania. Examples condensation reaction of 2-7 characterize titania surface EDA and DETA. areas of 51, 60 and 120 m.sup.2 /gm. Japanese Patent Group IVB metal oxide with Ammonia and MEA. Application bonded phosphorus. #1985-078,391, Publication #1986-236,752 Japanese Patent Group IVB metal oxide with Ammonia and MEA. Application bonded phosphorus. #1985-078,392, Publication #1986-236,753 U.S. Pat. No. 4,698,427 Titania having phosphorus Diethanolamine and/or thermally chemically bonded hydroxyethyldiethylene- to the surface thereof in the triamine in EDA. form of phosphate bonds. U.S. Pat. No. 4,806,517 Pelleted Group IVB metal oxide MEA and EDA. with phosphorus thermally chemically bonded to the surface thereof. European Patent Titania and zirconia chemically MEA and EDA. Application bonded to phosphorus. 331,396 __________________________________________________________________________
A summary of additional prior art for making alkyleneamines is set forth in Table II below.
TABLE II __________________________________________________________________________ CITATION CATALYST TYPE REACTANTS __________________________________________________________________________ Japanese Patent Niobium-containing Ammonia, alkyleneamine Application substance. and alkylene glycol. #1987-312,182, Publication #1989-153,659 Japanese Patent Niobium-containing Ammonia, alkyleneamine Application substance added and alkanolamine. #1987-325,274, to water-containing liquid. Publication #1989-168-647 Japanese Patent Niobium oxide Ammonia, alkyleneamine Application obtained from and alkanolamine #1987-321,348, niobium alkoxide. Publication #1989-163,159 Japanese Patent Niobium pentoxide. Ammonia, alkyleneamine Application and dialkanolamine. #1989-314,132, Publication #1989-157,936 Japanese Patent Niobium-containing Ammonia, alkyleneamine Application substance. and alkanolamine. #1987-290,652, Publication #1989-132,550 Japanese Patent Tantalum-containing Ammonia, alkyleneamine Application substance. and alkanolamine. #1987-142,284, Publication #1988-307,846 European Patent Mixed oxide Ammonia, alkyleneamine Application containing niobium and alkanolamine. 315,189 oxide. European Patent Niobium-containing Ammonia, alkyleneamine Application substance supported and alkanolamine. 328,101 on a carrier. Japanese Patent Titania and zirconia MEA and EDA. Application chemically bonded with #1989-048,699, phosphorus in the form Publication of a hydroxy-containing #1990-006,854 phosphate group. Japanese Patent Niobium oxide and titania, Ammonia, alkyleneamine Application alumina, silica or zirconia. and alkanolamine. #1988-262,861, Publication #1990-002,876 Japanese Patent Niobium oxide treated with Ammonia, alkyleneamine Application an acid. and alkanolamine. #1988-290,106, Publication #1990-000,735 Japanese Patent Niobium-containing Ammonia, alkyleneamine Application substance on a carrier. and alkanolamine. #1988-027,489, Publication #1990-000,736 Japanese Patent Three constituent catalyst- Alcohol or aldehyde and Application copper; one or more elements ammonia, a primary #1988-261,366 selected from chromium, amine or a secondary amine. Publication manganese, iron and zinc; #1990-000,232 and a platinum group element. Japanese Patent Four constituent catalyst-copper; Alcohol or aldehyde Application one or more elements selected and ammonia, a primary #1988-261,368, from chromium, manganese, iron, amine or a secondary amine. Publication cobalt, nickel and zinc; #1990-000,233 a platinum group element; and one or more elements selected from lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium and barium. Japanese Patent Four constituent catalyst-copper; Alcohol or aldehyde and Application one or more elements selected from ammonia, a primary amine #1988-261,369, chromium, manganese, iron, cobalt, or a secondary amine. Publication nickel and zinc; a platium group #1990-000,234 element; and one or more elements selected from aluminum, tungsten and molybdenum. __________________________________________________________________________
A market demand for PEHA and HETETA has been progressively developing in recent years. It would be desirable to satisfy this developing demand from a cost standpoint by modifying slightly the commercial processes directed to the manufacture of polyalkylene polyamines from suitable starting raw materials to the production of PEHA and HETETA as major products.
It would be desirable to have continuously produced compositions, generated by the reaction of dihydroxyethylethylenediamine (DiHEED) and EDA or other suitable starting raw materials over a fixed bed of a condensation catalyst under commercial conditions, that are rich in PEHA and HETETA and that are not disproportionately high in cyclics.
The above features are provided by this invention.